WO2013076175A1 - Psa contenant des copolymères blocs oléfiniques et des copolymères blocs styréniques - Google Patents

Psa contenant des copolymères blocs oléfiniques et des copolymères blocs styréniques Download PDF

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Publication number
WO2013076175A1
WO2013076175A1 PCT/EP2012/073293 EP2012073293W WO2013076175A1 WO 2013076175 A1 WO2013076175 A1 WO 2013076175A1 EP 2012073293 W EP2012073293 W EP 2012073293W WO 2013076175 A1 WO2013076175 A1 WO 2013076175A1
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WO
WIPO (PCT)
Prior art keywords
hot melt
melt adhesive
adhesive
block copolymers
copolymers
Prior art date
Application number
PCT/EP2012/073293
Other languages
German (de)
English (en)
Inventor
Eckhard Pürkner
Annie Seiler
Original Assignee
Henkel Ag & Co. Kgaa
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Henkel Ag & Co. Kgaa filed Critical Henkel Ag & Co. Kgaa
Priority to ES12790893T priority Critical patent/ES2828480T3/es
Priority to EP12790893.7A priority patent/EP2782969B1/fr
Priority to CN201280056951.XA priority patent/CN103946332B/zh
Priority to MX2014006138A priority patent/MX354708B/es
Priority to IN3686CHN2014 priority patent/IN2014CN03686A/en
Priority to CA2856710A priority patent/CA2856710C/fr
Priority to BR112014012114A priority patent/BR112014012114A8/pt
Priority to KR1020147013666A priority patent/KR102036390B1/ko
Priority to JP2014542820A priority patent/JP6152385B2/ja
Publication of WO2013076175A1 publication Critical patent/WO2013076175A1/fr
Priority to US14/284,770 priority patent/US9732258B2/en

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J147/00—Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds; Adhesives based on derivatives of such polymers
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J153/00—Adhesives based on block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Adhesives based on derivatives of such polymers
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J153/00—Adhesives based on block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Adhesives based on derivatives of such polymers
    • C09J153/02—Vinyl aromatic monomers and conjugated dienes
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J193/00—Adhesives based on natural resins; Adhesives based on derivatives thereof
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J7/00—Adhesives in the form of films or foils
    • C09J7/30—Adhesives in the form of films or foils characterised by the adhesive composition
    • C09J7/38—Pressure-sensitive adhesives [PSA]
    • C09J7/381—Pressure-sensitive adhesives [PSA] based on macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds
    • C09J7/387—Block-copolymers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L23/18—Homopolymers or copolymers of hydrocarbons having four or more carbon atoms
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L53/00—Compositions of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
    • C08L53/02—Compositions of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers of vinyl-aromatic monomers and conjugated dienes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L93/00—Compositions of natural resins; Compositions of derivatives thereof

Definitions

  • PSA containing olefin block copolymers and styrenic block copolymers PSA containing olefin block copolymers and styrenic block copolymers
  • the invention relates to hotmelt adhesives prepared based on olefin block copolymers and styrene block copolymers which are suitable together with other additives as pressure-sensitive hotmelt adhesive.
  • Hot melt adhesives suitable for bonding a wide variety of materials are well known.
  • EP 0912646 describes hot melt adhesives prepared from a substantially linear copolymer of ethylene together with at least one C3 to C2o ⁇ -olefin monomer.
  • hot melt adhesives are prepared based on linear ethylene- ⁇ -olefin copolymers. There are described the usual additional components, e.g. tackifying resins, waxes, other various polymers, styrenic block copolymers, plasticizers or other additives.
  • the intended use describes the bonding of paper and cardboard materials as well as use as adhesive tape or bookbinding. Olefinic block copolymers are not described.
  • WO 2006/102150 describes adhesives based on selected C 2 - ⁇ -olefin copolymers. These copolymers and their preparation are also described, for example, in WO 2005/090426. Special catalysts or carrier compounds are mentioned here. Apart from other products, adhesives are also described. It should be noted, however, that the composition of the constituents of the adhesives, their properties and their specific applications are listed only in the form of lists, enumerations and tasks. A clear disclosure of particular adhesive compositions is not given. Various general properties are described, in particular the viscosity.
  • WO 2005/028584 describes hot melt adhesives containing polyolefin polymers prepared by metallocene catalysis. These polymers should have a viscosity up to 9000 mPas at a temperature of 149 ° C, the hot melt adhesive itself a viscosity below 2000 mPas.
  • melt adhesives can be prepared.
  • the olefin copolymers can be varied within wide limits.
  • Styrenic block copolymers are also widely available commercially. They can be produced in a wide range of properties, in particular they are elastic polymers.
  • olefin copolymers are not sufficiently compatible with styrene block copolymers. This leads in practice to the fact that adhesives from such mixtures are not storage-stable or when applied in the melt. The polymers may partially segregate, then they are not applicable, or migrate to the surface and thus reduce the adhesion to the substrates later. As a result, such mixtures are not suitable as permanently tacky pressure-sensitive hot-melt adhesive.
  • styrene block copolymers do not give sticky surfaces. For example, if the tackiness is increased by plasticizers, the cohesion is reduced so that an adhesive layer breaks and the bond fails.
  • hot melt adhesives which consist of a mixture of olefin block copolymers and styrene block copolymers.
  • the hot melt adhesives should exhibit a suitable viscosity to allow application in a thin layer and on temperature sensitive substrates.
  • the layers obtained should show pressure-sensitively adhesive properties which are not impaired by the storage of the adhesive. the.
  • the adhesive layers should show a good elastic behavior in the bond.
  • a hot-melt adhesive containing (i) 15 to 70 wt .-% of a mixture of at least one copolymer based on ethylene and / or propylene and optionally at least one C4 to C20- ⁇ -olefin, by metallocene catalyzed polymerization is obtainable as a block copolymer and at least one styrene block copolymer, (ii) - 10 to 70 wt .-% of at least one tackifying resin, (iii) 0 to 40 wt .-% further additives and plasticizers, wherein the sum of the% - shares 100 % and the tackifying resin is wholly or partially a soft resin that is liquid at a temperature below 50 ° C.
  • Another object of the invention is the use of such hot melt adhesives for coating films, tapes, labels and other flat SubStarten to produce a pressure sensitive adhesive layer.
  • Another object of the invention are films, adhesive tapes and labels having on at least one side an adhesive layer of an adhesive according to the invention.
  • a necessary constituent of the pressure-sensitive hot-melt adhesive according to the invention are olefin copolymers based on ethylene and at least one C3 to C20- ⁇ -olefin. These polyolefins are prepared via metallocene catalysis. One embodiment of the invention uses such co- or terpolymers based on ethylene together C4 to C20 alpha-olefins.
  • the monomers which may be used in addition to ethylene or propylene are the known olefinically unsaturated monomers copolymerizable with ethylene or propylene.
  • ⁇ -olefins such as butene, hexene, methylpentene, octene; cyclic unsaturated compounds such as norbornene or norbornadiene; symmetrically or asymmetrically substituted ethylene derivatives, being suitable as substituents C1 to C12-alkyl radicals; and optionally unsaturated carboxylic acids or carboxylic anhydrides.
  • These may be homopolymers, copolymers, terpolymers, which also may contain other monomers. In the following, copolymers should also be understood as meaning those polymers of more than 2 monomers.
  • the amount of ⁇ -olefin comonomer should preferably be below 20%.
  • Another embodiment contains copolymers based on ethylene and propylene.
  • additional small proportions of C4 to C20- ⁇ -olefins are included. These are also prepared via metallocene catalysts.
  • the amount of propylene should be above 60 wt .-%, in particular, the proportion of propylene is above 70 wt .-%. If appropriate, small amounts of other ⁇ -olefin monomers may still be present, the amount should be less than 5%, but in particular ethylene / propylene block copolymers are suitable.
  • the (co) polymers thus obtained have a molecular weight of from 2,000 to 250,000 g / mol, in particular from 5,000 to 100,000 g / mol (number average molecular weight, M n , determined by GPC). These (co) polymers are characterized by having a narrow molecular weight distribution.
  • the molecular weight distribution expressed as M W / M N should be, for example, up to 2.5, in particular below 2.3.
  • suitable polymers are commercially available under the tradename Vistamax® or Infuse®.
  • the copolymers which are suitable according to the invention are block copolymers.
  • the blocks have a different composition of the monomers.
  • the hot-melt adhesives suitable according to the invention have a glass transition temperature
  • the copolymers should have two glass transition temperatures.
  • the first glass transition temperature (Tg) (measured by DTA) should be in the range between -100 to 0 ° C, in particular between -80 to -10 ° C.
  • the second glass transition temperature should be below -100 ° C in particular.
  • those olefinic block copolymers are suitable which are prepared by catalysis with metallocene compounds.
  • the melt index of these polymers should be from 5 g / 10 min to 200 g / 10 min, preferably up to 100 g / 10 min (measured at 190 ° C, 2.16 kg, DIN ISO 1 133).
  • the softening point of the polymers should be above 130 ° C., in particular above 160 ° C.
  • the amount of these copolymers should be 5 to 50 wt .-% based on the hot melt adhesive, in particular between 15 to 30 wt .-%.
  • the (co) polymer may be a polymer, but it is also possible that a mixture is used.
  • a pressure-sensitive hot-melt adhesive (PSA) according to the invention must contain at least one thermoplastic elastic styrene block copolymer. These are preferably triblock copolymers, but it is also possible to use diblock copolymers or else mixtures of both types. Such block copolymers are poorly compatible with the olefin block copolymers.
  • They may be different types of styrenic block copolymers.
  • styrene-isoprene block copolymers SIS
  • SIBS styrene-isoprene-butadiene block copolymers
  • SBS styrene-butadiene block copolymers
  • hydrogenated forms of the copolymers such as SBBS, SEBS, SEPS, SIPS or mixtures thereof, and corresponding diblock copolymers.
  • M N molecular weight
  • the amount of the styrene block copolymers contained in addition to the olefin block copolymers is from 3 to 35% by weight, in particular from 5 to 25% by weight, based on the hotmelt adhesive.
  • the amount of these block copolymers influences the elasticity of the adhesive. If the amounts of block copolymers are too high, the adhesive is too elastic and can be processed poorly. In addition, increased intolerances are observed, the lead to poor adhesive properties. If the amount is too small, the cohesion of an adhesive layer is reduced.
  • the pressure-sensitive hot-melt adhesive according to the invention comprises at least one tackifying resin.
  • the resin causes additional stickiness of the adhesive. It is used in an amount of 10 to 60 wt .-%, preferably 10 to 40 wt .-%.
  • the resins at least partially contain a soft resin which is liquid or flowable below 50 ° C. This can be determined by the dropping temperature.
  • Resins can be selected from aromatic, aliphatic or cycloaliphatic hydrocarbon resins, as well as modified or hydrogenated derivatives.
  • resins which can be used in the context of the invention are polyterpene resins, phenolic or aromatic modified polyterpene resins, modified natural resins such as resin acids from gum rosin, tall resin or wood rosin, optionally also hydroabietyl alcohol and its esters, acrylic acid copolymers such as styrene-acrylic acid copolymers and resins based on functional resins hydrocarbon resins.
  • Typical resins have a low molecular weight of below 2000 g / mol, in particular below 1500 g / mol. They may be chemically inert or they may optionally also contain functional groups, such as, for example, OH groups, carboxyl groups or double bonds.
  • soft resins should be selected which have a dropping temperature below 50 ° C., in particular below 35 ° C. (Mettler dropping point according to ASTM D-3104).
  • additional resins it is also possible to add those resins which have a softening point between 70 and 130 ° C. (Ring Ball method, DIN 5201 1). It is preferred to use rosin resins and in particular fully or partially hydrogenated hydrocarbon resins.
  • the amount of the resins solid at room temperature may be up to 50% of the total resin amount.
  • Plasticizers are preferably used to adjust viscosity or flexibility and are generally contained in a concentration of 0-25% by weight, preferably 2-15% by weight.
  • Suitable non-polar plasticizers include synthetic oils, paraffinic oils, naphthenic oils or polyisobutylenes. These are, for example, medicinal white oils, naphthenic mineral oils, polypropylene, polybutene, polyisoprene oligomers, hydrogenated polyisoprene and / or polybutadiene oligomers, paraffinic hydrocarbon oils.
  • the sum of the soft resin and the plasticizer is from 10 to 35% by weight.
  • additives are contained in the hot-melt pressure-sensitive adhesive according to the invention, which can influence certain properties of the adhesive, such. Cohesive strength, viscosity, softening point or processing viscosity. These include, for example, stabilizers, waxes, adhesion promoters, antioxidants, light stabilizers, color pigments, rheology agents or similar additives. The amount should be up to 15% by weight. It is also possible to use several additives as a mixture. Furthermore, fillers can be used to increase the strength. For adjusting the properties, even small amounts of plasticizers may be added as glycerol, benzoate or phthalate esters or polyglycol ethers.
  • waxes in amounts of 0 to 5 wt .-% can be added to the pressure-sensitive hot-melt adhesive.
  • the amount is so dimensioned that on the one hand the viscosity is adjusted, but on the other hand the adhesion is not adversely affected.
  • the wax can be of natural or synthetic origin. Vegetable waxes, animal waxes can be used as natural waxes, mineral waxes or petrochemical waxes as synthetic waxes. Preferably waxes should not be included.
  • antioxidants Another group of additives are stabilizers. Their task is to protect the polymers from degradation during processing. Here are in particular the antioxidants to call. They are usually added in amounts of up to 3% by weight, preferably in amounts of from about 0.1 to 1.0% by weight, to the hot-melt pressure-sensitive adhesive. Such additives are known to those skilled in principle. He can make a selection according to the desired properties of the hot melt adhesive.
  • the pressure-sensitive hot-melt adhesive according to the invention can contain adhesion-curing agents.
  • Bonding agents are substances that improve the adhesion of the hotmelt adhesive to the substrate to be bonded.
  • adhesion promoters should improve the aging behavior of bonds under the influence of humid atmosphere.
  • Typical adhesion promoters are, for example, ethylene / acrylamide comonomers, polymeric isocyanates, reactive organosilicon compounds or phosphorus derivatives.
  • the wetting properties of the adhesive and thus the adhesion to the substrates can be influenced.
  • a preferred embodiment of the pressure sensitive hotmelt adhesive comprises 15 to 30% by weight of a block copolymer based on ethylene and / or propylene and optionally at least one C 4 to C 20 ⁇ -olefin obtainable by metallocene-catalyzed polymerization, and 5 to 35% by weight.
  • % of at least one styrenic block copolymer from 5 to 35% by weight of at least one tackifying resin which is liquid below 50 ° C, from 0 to 25% by weight of a nonpolar plasticizer and from 0 to 15% by weight of other additives, the sum % shares should be 100%.
  • the pressure-sensitive hot-melt adhesive according to the invention is prepared by melt-mixing by known processes. In this case, all components can be presented simultaneously, heated and then homogenized, or it is first presented the lighter-melting components and mixed, then added the other resin components. It is also possible to produce the hot melt adhesive continuously in an extruder.
  • the suitable hotmelt adhesive is solid and, except for impurities, free from solvents.
  • the inventively suitable hot melt adhesive should have a viscosity of 3000 to 50,000 mPas, preferably from 5000 to 30,000, in particular about 10000 mPas measured at application temperature. This is between 140 and 190 ° C (Brookfield, EN ISO 2555, measured at specified temperature).
  • the pressure-sensitive hot-melt adhesives according to the invention are suitable for joining a wide variety of materials.
  • materials such as polyolefin films, for example polyethylene films or polypropylene films, polyolefin nonwovens, for example polyethylene nonwovens or polypropylene nonwovens, polyurethane films, polyurethane foams, films of cellulose derivatives, films of polyacrylates or polymethacrylates, films of polyester, in particular polylactide, polycaprolactone, polyesteramide can be interconnected.
  • the molten adhesive is applied to a substrate and then glued to a second substrate.
  • Another preferred embodiment carries the adhesives of the invention as an adhesive layer on a support.
  • the carriers are the known flexible films which are also suitable as adhesive tape. These non-tacky films are coated on one or both surfaces with a hotmelt adhesive according to the invention.
  • the layer thickness of the applied adhesive is for example from 50 to 500 g / m2 (about 50 to 500 ⁇ ). In particular, the layer thickness should be from 100 to 350 g / m2.
  • Such adhesive layers have good adhesion to the substrate.
  • Such carrier films usually have an anti-adhesion coated backside that can be easily separated from the pressure-sensitive adhesive layer.
  • a specific use form of the hot-melt adhesives according to the invention is the coating of self-adhesive films, tapes or labels with an adhesive layer.
  • tapes or films for example based on polyolefins or polyesters, coated with the present invention suitable hot melt adhesive.
  • a permanent pressure-sensitive adhesive layer is obtained by selecting a suitable adhesive. Thereafter, these materials can be made up. In this way, permanently adhesive results can be lien, labels and tapes.
  • the self-adhesive surfaces thus obtained may optionally be covered by anti-adhesively coated materials.
  • the adhesives of the invention are cloudy. At room temperature, a layer of 1 cm thickness is opaque. However, there is no floating of individual components, so that the adhesive force of the non-bonded layer or bonded substrates is not reduced. In the melt adhesives of the invention are stable, there is no phase separation even after prolonged storage in the molten state.
  • the adhesives used according to the invention show good tack.
  • the layers are elastic and show good cohesive cohesion.
  • the two block copolymers form a stable mixture which does not lead to phase separation. In this case, a high adhesion is obtained.
  • the adhesives of the invention are known as a coating for film application.
  • Corresponding coated products can be used in many fields of application, for example as adhesive tapes or labels, multilayer films for use as fasteners, for packaging, in hygiene products or in medical applications.
  • Viscosity 15300 mPas, 170 ° C
  • the adhesive is solid or melted in a thin layer cloudy (visual assessment).
  • a carrier film (PE, 50 ⁇ ) is coated with about 250 g.
  • the adhesion remains constant even after storage, there is no exudation of the incompatible components.
  • Viscosity 51200 mPas, 170 ° C
  • the adhesive is solid or melted in a thin layer cloudy (visual assessment).
  • the bond strength of a coated film is low (measured as loop tack, ASTM D6195).
  • Viscosity 42700 mPas, 150 ° C
  • Viscosity 19200 mPas, 170 ° C
  • the bond strength of a coated film (loop tack) is low.

Abstract

L'invention concerne des adhésifs thermofusibles ("hotmelt") stables au stockage, contenant 15 à 70 % en poids d'un mélange constitué d'au moins un copolymère à base d'éthylène et/ou de propylène et d'au moins une -α-oléfine en C4-C20, lequel peut être obtenu sous forme de copolymère bloc par polymérisation catalysée par des métallocènes, et d'au moins un copolymère bloc styrénique, 10 à 70 % en poids d'au moins une résine tackifiante et 0 à 40 % en poids d'autres additifs, la somme des pourcentages devant être égale à 100 % et tout ou partie de la résine tackifiante étant une résine molle.
PCT/EP2012/073293 2011-11-22 2012-11-22 Psa contenant des copolymères blocs oléfiniques et des copolymères blocs styréniques WO2013076175A1 (fr)

Priority Applications (10)

Application Number Priority Date Filing Date Title
ES12790893T ES2828480T3 (es) 2011-11-22 2012-11-22 PSA que contiene copolímeros de bloque de olefinas y copolímeros de bloque de estireno
EP12790893.7A EP2782969B1 (fr) 2011-11-22 2012-11-22 Psa contenant des copolymères blocs oléfiniques et des copolymères blocs styréniques
CN201280056951.XA CN103946332B (zh) 2011-11-22 2012-11-22 包含烯烃嵌段共聚物和苯乙烯嵌段共聚物的psa
MX2014006138A MX354708B (es) 2011-11-22 2012-11-22 Psa que contiene copolimeros en bloque de olefinas y copolimeros en bloque de estireno.
IN3686CHN2014 IN2014CN03686A (fr) 2011-11-22 2012-11-22
CA2856710A CA2856710C (fr) 2011-11-22 2012-11-22 Psa contenant des copolymeres blocs olefiniques et des copolymeres blocs styreniques
BR112014012114A BR112014012114A8 (pt) 2011-11-22 2012-11-22 psa contendo copolímeros em bloco de olefinas e copolímeros em bloco de estireno
KR1020147013666A KR102036390B1 (ko) 2011-11-22 2012-11-22 올레핀 블록 공중합체 및 스티렌 블록 공중합체를 함유하는 ｐｓａ
JP2014542820A JP6152385B2 (ja) 2011-11-22 2012-11-22 オレフィンブロックコポリマーおよびスチレンブロックコポリマーを含有するｐｓａ
US14/284,770 US9732258B2 (en) 2011-11-22 2014-05-22 PSA containing olefin block copolymers and styrene block copolymers

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE102011086845A DE102011086845A1 (de) 2011-11-22 2011-11-22 PSA enthaltend Olefinblockcopolymeren und Styrolblockcopolymere
DE102011086845.3 2011-11-22

Related Child Applications (1)

Application Number Title Priority Date Filing Date
US14/284,770 Continuation US9732258B2 (en) 2011-11-22 2014-05-22 PSA containing olefin block copolymers and styrene block copolymers

Publications (1)

Publication Number Publication Date
WO2013076175A1 true WO2013076175A1 (fr) 2013-05-30

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PCT/EP2012/073293 WO2013076175A1 (fr) 2011-11-22 2012-11-22 Psa contenant des copolymères blocs oléfiniques et des copolymères blocs styréniques

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Country Link
US (1) US9732258B2 (fr)
EP (1) EP2782969B1 (fr)
JP (1) JP6152385B2 (fr)
KR (1) KR102036390B1 (fr)
CN (1) CN103946332B (fr)
BR (1) BR112014012114A8 (fr)
CA (1) CA2856710C (fr)
DE (1) DE102011086845A1 (fr)
ES (1) ES2828480T3 (fr)
IN (1) IN2014CN03686A (fr)
MX (1) MX354708B (fr)
PT (1) PT2782969T (fr)
WO (1) WO2013076175A1 (fr)

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CN103709962A (zh) * 2013-12-04 2014-04-09 浙江固特热熔胶有限公司 鞋胶及其生产方法
CN104031586A (zh) * 2014-05-29 2014-09-10 浙江固特热熔胶有限公司 高低温通用型热熔压敏胶及其制备方法
CN104610891A (zh) * 2015-01-29 2015-05-13 广东聚胶粘合剂有限公司 一种具有优异热稳定性的热熔压敏胶
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PT2782969T (pt) 2020-10-15
CN103946332A (zh) 2014-07-23
DE102011086845A1 (de) 2013-05-23
ES2828480T3 (es) 2021-05-26
EP2782969B1 (fr) 2020-10-07
US9732258B2 (en) 2017-08-15
CN103946332B (zh) 2018-03-27
IN2014CN03686A (fr) 2015-07-03
MX2014006138A (es) 2014-08-27
JP6152385B2 (ja) 2017-06-21
CA2856710A1 (fr) 2013-05-30
KR20140094558A (ko) 2014-07-30
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BR112014012114A8 (pt) 2017-06-20
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